Metallized monoazo dyes



United States Patent O 3,201,383 METALLIZED MONOAZQ DYES James M. Straley and Raymond C. Harris, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey N Drawing. Filed July 5, 1962, Ser. No. 207,792 6 Claims. (Cl. 260-147) This invention relates to a class of metallized monoazo compounds obtainedby metallizing the dyes obtained by coupling the diazo salt of N'y-dialkylaminoalkyl-4- methoxy 3 aminobenzenesulfonamides with 5 pyrazolones free of carboxylic and sulfonic acid radicals yielding compounds imparting fast yellow shades particularly to acrylic fibers. The metallized dyes are characterized by producing shades on these fibers more fast than obtained with the dyes in the metal-free state.

While our invention relates broadly to the metallized monoazo compounds, a preferred group of metallized compounds are the nickel, cobalt, chromium and copper complex unions with two moles of azo dyes having the following general formula:

OCH3

jwherein Pz represents a 4-pyrazolyl-5-one radical free of carboxy and sulfo groups and preferably containing a phenyl radical in the l-position e.g. phenyLfi-hydroxyethylphenyl, chlorophenyl, tolyl, methoxyphenyl, nitrocabomethoxy-S-pyrazolone,

3.,2el,383 Patented Aug. 17, 1%65 copper compounds. Thus, nickel chloride, nickel bromide, nickel sulfate, nickel acetate, nickel cyanide, nickel formate, nickel thiocyanate ,[Ni(SCN) cobaltous bromide, cobalticichloride, cobaltous chloride, cobaltous acetate, cobaltous cyanide, cobalt thiocyanate tc e Nm ferric thiocyanate [Fe(SCN)3] and vanadium thiocyanate [V(SCN) are illustrative of the metallizing agents that can be employed.

S-pyrazoles useful in preparing the monoazo dye are: 3-methyl-5-pyrazolone, 3-carboXy-5-pyrazolone, 3-

3-carboethoxy-S-pyrazolone,

The metallized monoazo compounds of our invention a are prepared by treating the non-metallized monoazo compounds with for example salts of nickel, cobalt, copper, chromium, manganese, iron' or vanadium. The non-metallized monoazo compounds can be metallized either on or off the fiber. Metallization can be carried out, for example, by treating the nonmetallized dye with a solution or dispersion of the metallizing agent. Although the metal complex is often formed at room temperature, we prefer to accelerate the process by heating, usually with steam, for a short time. tion of the metallized monoazo compounds of our invention is fully described hereinafter.

Illustrative of the metallizing agents that can be employed are the halides, the sulfates, the acetates, the cyanides, and the thiocyanates of nickel, cobalt, chromium, manganese, iron and vanadium as well as various The prepararomethyl-S-pyrazblone, 1-phenyl-3-methyl5-pyrazoione,

5 1 phenyl 3 amino 5 pyrazolone, 1 phenyl 3 hiydroxy-S-pyrazolone, 1-(2 benzothiazolyl)-3 amino-5-pyrazolone, 1-phenyl-3-methyl-5-p-nitrophenyl pyrazolone, 3-phenyl-5-pyrazolone, 1-phenyl-3-carbometh0Xy-5-pyrazolone, 1-phenyl-3-carbomethoxy-S-pyrazolone, 1,3-dimethyl-S-pyrazol-one, 1-p-nitrophenyl-3-methyl-5-pyrazolone, 1-o-nitrophenyl-3-methyl-5-pyrazolone, l-p-methylphenyl 3 methyl 5 pyrazolone, l p methoxyphenyl-3-amino-5-pyrazolone, l-p-methylphenyl-3-amino-5-py- 'razolone, l-o-chlorophenyl-3-amino-5-pyrazolone, l-pchlorophenyl 3 amino 5 pyrazolone, 1 p ethylphenyl 3 methyl 5 pyrazolene, 1 p chlorophenyl- 3-methyl-5-pyrazolone, 1-(2-benz0thiazoly)-3-methyl-5- pyrazolone, 1 -(2 benzothiazolyl) 3 carbOmethOXy-S- pyrazolone, 3-isobutyl-l-phenyl-S-pyrazolone, 3-phenyl-lfi-hydroxyethyl-5-pyrazolone and 1-phenyl-3-amino-5- pyrazolone Representative sulfonamides useful for diazotization and coupling with the S-pyrazolones above are as follows:

N-B-diethylaminoethy1-4-methoxy-3-aminobenzenesulfonamide N-fi-dimethylaminoethylt-methoxy-3-aminobenzenesulfcnamide N-fi-dibutylaminoethyl-4-methoxy-S-aminobenzenesulfonamide N-B-dimethylaminopropyl-4-methoXy-3 -aminobenzenesulfonamide N-fi-dimethylaminomethyl-4 methoxy-3-aminobenzenesulfonamide N-B-dipropylaminopropyl-4-methoXy-3 -aminobenzenesulfonamide As mentioned above, the metallized dyes are particularly useful for dyeing acrylic fibers such as polyacrylonitrile copolymers of acrylonitrile and graft polymers of acrylonitrile e.g. vinylidene chloride-acrylonitrile copolymers and acrylamide-acrylonitrile copolymers.

The following table shows the colors obtainable by dyeing acrylic fibers with representative metallized [with Ni] dyes of the invention having the above general formula.

5Pyrazolone Used R R1 R1 Color 1,3-diphenyl -C3H1 Yellow.

-CH3 D0. CH3 D0. 3-methyl-l-[2,4,G-trichloro- -[CH2]3 CH3 Do. agtyi when 1 orn]3 OHa Do. S-n-propyl -[CH2}3 CH3 D0. 3-phenyl-l-B-hydroxyethyl -[CHaa OH3 Do.

CHzCEQ 1-pl1enyl-3-methyl -[CHz]3- NR1R2=N D0.

CHz-C o [OH1}3 NR1R2=N-piperidino D0.

D0 -[CH2 s- -CH3 D0. l-phenyl-ii-isobutyl. [CHa]s CHa Do. l-fl-hydroxyethyl'ii-p [CH2]s CH3 D0. 3-meth l [CH2]z- C2H5 D0. 1-phenyl-3-amin0 [CH2]z --OII3 Do.

The following examples will serve to illustrate our in- Example 5 Exampk 1 5.14 g. 0.01 mole) of the dye obtained by coupling N- 'y-dimethylaminopropyl 4 methoxy-3-aminobenesulfon- Three and seven tenths grams [0.01 m.] of N-lx-diamide to 3-isobutyl-l-phenyl-S-pyrazolone as in Example methylaminopropyl-4-methoxy-3-amino benzenesulfon- 1, is heated to 60 C. in 100 cc. of methyl Cellosolve. A amide dihydrochloride is dissolved in cc. of water and solution of 2.55 g. Ni(OCOCH -4H O in 25 cc. of wa- 7 cc. conc. HCl, cooled to 0 C. and diazotized by the ter is added and the solution stirred at reflux for 5 hours. addition of 0.7 g. NaNO in 5 cc. of water. After 1 After cooling it is drowned in 1500 cc. of Water containing hour of further stirring below 5 C. the excess HNO 30 15 cc. of 28% NH OH. Sodium chloride is stirred in was destroyed with sulfamic acid. In the meantime a couuntil the dispersion is broken and the solid filtered 01f, pler solution was prepared by dissolving 1.74 g. Z-methylwashed with water and dried. The product imparts fast l-phenyl-S-pyrazolone in 50 cc. of 2% NaOH and bringyellow shades to acrylonitrile polymer fibers. ing to 0 C. by addition of crushed ice. The diazo was stirred in and stirred for 1.5 hours. The acid was neutral- Example 6 ized with sodium bicarbonate, and the product filtered off 5'02 (001 mole) of the dye from the diam of EXam and Washed with water. After drying at 60 4.55 g. of p16 5 and 3 pheny1 1 p hydroxyethyl 5 pyrazo1one is yellow S0114 f when metalhzed Wlth or CO on treated as in Example 5, using as the metal salt 2.55 g. of

' acryhc fabnc mparts yellow Shades C0(OCOCH -4H O. The product imparts to the fibers The dye has the followmg formula 40 slightly redder shades than in Example 5.

00m Example 7 9.44 g. (0.02 mole) of the product of Example 1 is HO N added in small portions to a freshly prepared solution of 10.8 g. CrCl -6H O in 100 cc. of ethylene glycol at 140 N C. After addition the solution is stirred one hour longer H3)2N( 2)3 2 (3. 11 at this temperature, cooled to 80 C. and poured into 220 cc. of water. The solution is made basic with NH OH Example 2 and 30 g. of NaCl is stirred in. The product is filtered 1 oil, washed with 5% salt solution, then water and air- One and elghieen hundreflths grams [Q0025 In] of dried. The dye imparts fast orange shades to acrylonithe product of Example 1, 15 cc. of acetone and 2 cc. u polymfir fibem 28% NH OH is brought to reflux. A solution of 0.7 g. Example 8 Ni[OAc] -4H O in 15 cc. of 50% aqueous acetone is added and refluxing continued for 2.5 hours. The mix 2.35 g. (0005 H1016) 0f the pro t 0f E mple was drowned in 400 cc. of water, 20 g. salt added, brought 1.24 g. Cu(NO -3H O, 0.26 g. Na CO and 20 cc. of to 75 C. and allowed to cool. The solid was filtered methyl Cellosolve are heated in 1 hour to reflux and off, Washed with salt solution and air-dried. It imparts stirred 4 hours at this temperature. After cooling and fast yellow shades to acrylonitrile copolymer fiber. drowning in 100 cc. of water the product is filtered oil,

washed with salt solution and air-dried. Fast yellow shades Example 3 are imparted to acrylonitrile polymer fibers.

Three and eight tenths grams of N-fi-dimethylarnino- What We clan? 1s: ethyl-4-methoxy 3 aminobenzenesulfonamido dihydro- The metalhzed monoazo pq C({ntammg one chloride is diazotized and coupled as in Example 1 to atom 9 3 metal of the class conslstmg of P Cobalt 0.98 g. of 3-methyl-5-pyrazolone. The metallizcd nickel Chromlum and p In a F 16X umon Wlth two dyeings on acrylonitrile copolyrner fiber yield fast yellow moles of a dye havmg the followmg general formulashades.

Example 4 OCH? Three and five tenths grams of N-fi-dimethylamino- N=N"Pz methyl-4-methoxy-3-aminobenzenesulfonarnide dihydrochloride are diazotized and coupled as in Example 1 to 1.75 g. of 3-amino-l-phenyl-pyrazolone. The product 0 NH R metallized on the acrylonitrile copolyrner cloth with Ni or s P Co yields fast yellow dyeings. 7 5 RI wherein Pz==a 4-pyrazolyl-5-one radical free of carboxylic and sulfonic acid groups R=a lower alkylene radical R and R =1oWer alkyl radicals and together with the nitrogen atom to which they are attached represent the atoms necessary to complete a member of the class consisting of an N-morpholino radical and an N-piperidino radical. 2. The metallized monoazo compound containing one atom of nickel in a complex union with two moles of a dye having the formula 3. The metallized monoazo compound containing one atom of chromium in a complex union with two moles of the dye having the formula of claim 2.

4. The metallized monoazo compound containing one atom of copper in a complex union with two moles of the dye having the formula of claim 2.

5. The metallized azo dye containing one atom of nickel in a complex union with two moles of a dye having the formula OCHs 6. The metallized monoazo compound containing one atom of cobalt in complex union with two moles of a dye having the formula OCHz I a)2N( 2)aNH 2 12114011 References Cited by the Examiner UNITED STATES PATENTS 2,789,975 4/57 Ruckstuhl 260147 25 2,816,101 12/57 Brieg et al. 260-l47 3,045,003 7/62 Dehnert et al 260-147 CHARLES B. PARKER, Primary Examiner. 

1. THE METALLIZED MONOAZO COMPOUNDS, CONTAINING ONE ATOM OF A METAL OF THE CLASS CONSISTING OF NICKEL, COBALT, CHROMIUM AND COPPER, IN A COMPLEX UNION WITH TWO MOLES OF A DYE HAVING THE FOLLOWING GENERAL FORMULA. 